Vinylidene chloride resin plasticzed with a di-ester of endomethylene tetra-hydro phthalic acid



I Patented Sept; 21,1943

OFFICE! CIZED WITH A DI-ESTER F ENDO- METHYLENE TETltA-HYDBO PHTHAL- IC ACID Hanna Peter Staudinger, Ewell, Donald Faulkner, Cambridge, and George Thomas Wright, Manchester, England, assignors to lhe Distillers Company Limited, Edinburgh,

British company Scotland, a

No Drawing. Application January 2, 1945, Serial No. 571,110. In Great Britain December 8,

. Section 1, Public Law 890, August 8, 1948 Patent expires December 8, 1983 6 Claims. (Cl. 280-313) 1 This invention relates to improvements in com- .positions comprising vinylidene chloride polymers or copolymers and compounds whichact as stabilisers and plasticisers therefor.

Polymers oi vinylidene chloride, and its copolymers with other polymerisable materials, tend to decompose and discolour under the influence 01' heat and/or light. This is particularly unde- 'sirable when manipulating polyvinylidene chloride products by moulding or extrusion, since temperatures of the order 01' 170 C. to 200C. are required, at which temperatures a great amount 0! discolouration takes place. For this reason it is highly desirable to employ stabilisers which will prevent or at least minimise the decomposition and darkening effect.

It is therefore one object of the present invention toqprovide a vinylidene chloride polymeror copolymer having a lesser tendency to decompose or darken by exposure to heat and/or light as wherein R represents an alkyl, alkenyl, alkynyl, aralkyl or cycloaliphatic group, or any of the said groups containing also a halogen substituent.

The proportion of these estersemployed as stabilisers may vary from 1%30%, preferably, however, between 5% and 20%, oi the weight of the polymer. These stabilisers may be added to the powder and evaporating the inert solvent. Alternatively, the polymer may be milled on hot rollers with the stabilising compound either with or without the aid of a volatile dispersion media.

Particularly suitable esters are those derived from the lower alcohols such as ethyl or butyl alcohols or of the higher aliphatic alcohols such as hexyl and octyl alcohol. The esters may, however, also be prepared from unsaturated alcohols such as allyl, methallyl, chlorallyl and cinnamyl alcohols or even from alcohols containing an acetylenic linkage such as propargyl alcohol.

The following examples illustrate the manner in which the invention may be carried into effect.

Example 1.2 gms. polyvinylidene chloride are l mixed with 0.1 gm. of the 'diallyl ester of endo- ,cream colour while a disc moulded under identical conditions but without the addition of the endo-methylene-tetra-hydro-phthalic ester stabiliser was darkbrown and showed signs of decomposition. The discs were examined in ajKodak" colorimeter and the colour determined in reflected light. The disc stabilised in accordance with the.

invention gave a total colour of 9.5 yellow and red units, while the unstabilised disc made from polyvinylidene chloride and tricresyl phosphate alone gave a total of colour units.

Era'mple 2. gms. of a copolymer, prepared by polymerisation of a mixture of vinylidene chloride and diethyl maleate in the proportion of 9 to 1 respectively, were mixed with 4 gms. of dibutyl endomethyiene-tetrahydrophthalate. This mixture, which was still in the form of a powder, was then heated up to. 180 C. and extruded through a small orifice. The extruded string was of a very light brown colour and extrusion proceeded very smoothly. Higher temperatures had to be used to extrude the unstabilised material.

vinylidene chloride .polymer or copolymer by any known means, for example by dissolving it in a solvent, mixing this solution with the polymer Even before reaching the temperature of C. the unstabilised material started to discolour after about 5 minutes at this temperature The 3 colour of the unstabilised copolymer after this treatment was dark brown.

Example 3.-24 gms. of a co-polymer, prepared from 85 gins. of vinylidene chloride and 15 gms. of ethyl acrylate and having a. chlorine content of 60.0% by weight, were mixed with 3 gins. dihexyl sebacate and 3 gms. di-pi'opargyl-endomethylene-tetra-hydro-phthalate, dissolved in petrol ether (60/80 C. boiling range). After removal of the inert diluent, the powdery copolymer mix was'pressed between polished plates at 165 C. and under a pressure of about 1.5 tons per sq. inch, to give a transparent, tough sheet, showing no signs of discoloration.

Example 4.5 gms. of a 90/10 vinylidene chloride/vinyl chloride co-polymer were mixed with a solution of 0.75 gm. of dibutyl endomethylenetetra-hydro-iphthalate and' 0.5 gm. of tricresyl phosphate in 30 cos. ether. After evaporation of the ether. the powder was pressed in a copper mould at 170 C. for 2 minutes, to give a sheet of 1 mm. thickness. This sheet was free from bubbles and had a very light brown colour. When pressing a similar composition, in which the endowherein the esterifying radicles R. are the same and are selected from the group consisting of alkyl, alkenyl, aralkyl and alkynyl radicies, and wherein X is selected from the group consisting of hydrogen and halogen;

2. A composition according to claim 1 wherein said organic di-ester is present in an amount of from 5% to 20% by weight of the said resin.

3. A composition of matter comprising a vinylidene chloride/diethyl maleate copolymer and from 1 to 30% by weight of the copolymer of dibutyl endo-methylene-tetrahydrophthalate.

4. A composition of matter comprising about 87% by weight of polyvinylidene chloride, about 4% by weight of di-allyl endo-methylene-tetrahydrophthalate and about 90% by weight of tricresyl phosphate.

5. A composition of matter comprising about by weight of a vinylidene chloride/vinyl chloride copolymer, about 12% by weight of dibutyl endo-methylene-tetrahydrophthalate and about 8% by weight of tricresyl phosphate.

6. A hot moulded article formed from a. composition comprising a vinylidene chloride resin and from 1-30% by weight of the said resin 01 an organic di-ester of endo-methylene-tetrahydrophthalic acid of the formula REFERENCES CITED The following references are of record in the file of thispatent:

UNITED STATES PATENTS Name Date Stall? et a1 Feb. 16, 1943 Number 

